Improving devices incorporating solution-processed nanocrystal-based semiconductors requires a better understanding of charge transport in these complex, inorganic–organic materials. Here we perform a systematic study on PbS nanocrystal-based diodes using temperature-dependent current–voltage characterization and thermal admittance spectroscopy to develop a model for charge transport that is applicable to different nanocrystal-solids and device architectures. Our analysis confirms that charge transport occurs in states that derive from the quantum-confined electronic levels of the individual nanocrystals and is governed by diffusion-controlled trap-assisted recombination. The current is limited not by the Schottky effect, but by Fermi-level pinning because of trap states that is independent of the electrode–nanocrystal interface. Our model successfully explains the non-trivial trends in charge transport as a function of nanocrystal size and the origins of the trade-offs facing the optimization of nanocrystal-based solar cells. We use the insights from our charge transport model to formulate design guidelines for engineering higher-performance nanocrystal-based devices.

The potential of semiconductors assembled from nanocrystals has been demonstrated for a broad array of electronic and optoelectronic devices, including transistors, light emitting diodes, solar cells, photodetectors, thermoelectrics, and phase change memory cells. Despite the commercial success of nanocrystal quantum dots as optical absorbers and emitters, applications involving charge transport through nanocrystal semiconductors have eluded exploitation due to the inability to predictively control their electronic properties. Here, we perform large-scale, ab initio simulations to understand carrier transport, generation, and trapping in strongly confined nanocrystal quantum dot-based semiconductors from first principles. We use these findings to build a predictive model for charge transport in these materials, which we validate experimentally. Our insights provide a path for systematic engineering of these semiconductors, which in fact offer previously unexplored opportunities for tunability not achievable in other semiconductor systems.

Ternary I–III–VI nanocrystals, such as silver indium selenide (AISe), are candidates to replace cadmium- and lead-based chalcogenide nanocrystals as efficient emitters in the visible and near IR, but, due to challenges in controlling the reactivities of the group I and III cations during synthesis, full compositional and size-dependent behavior of I–III–VI nanocrystals is not yet explored. We report an amide-promoted synthesis of AISe nanocrystals that enables independent control over nanocrystal size and composition. By systematically varying reaction time, amide concentration, and Ag- and In-precursor concentrations, we develop a predictive model for the synthesis and show that AISe sizes can be tuned from 2.4 to 6.8 nm across a broad range of indium-rich compositions from AgIn11Se17 to AgInSe2. We perform structural and optical characterization for representative AISe compositions (Ag0.85In1.05Se2, Ag3In5Se9, AgIn3Se5, and AgIn11Se17) and relate the peaks in quantum yield to stoichiometries exhibiting ...

We report an approach to linearly upscale hot-injection syntheses of colloidal nanocrystals by applying mild underpressure to the flask reactor prior to the injection such that rapid addition of large volumes of the precursor is facilitated. We apply this underpressure-assisted approach to successfully upscale synthetic protocols for metallic (Sn) and semiconductor (PbS, CsPbBr₃, and Cu₃In₅Se₉) nanocrystals by 1–2 orders of magnitude to obtain tens of grams of nanocrystals per synthesis. Here, we provide the technical details of how to perform underpressure-assisted upscaling and demonstrate that nanocrystal quality is maintained for the large-batch syntheses by characterizing the size, size distribution, composition, optical properties, and ligand coverage of the nanocrystals for both small- and large-scale syntheses. This work shows that fast addition of large injection volumes does not intrinsically limit upscaling of hot-injection-based colloidal syntheses.

Phonon engineering of solids enables the creation of materials with tailored heat-transfer properties, controlled elastic and acoustic vibration propagation, and custom phonon–electron and phonon–photon interactions. These can be leveraged for energy transport, harvesting, or isolation applications and in the creation of novel phonon-based devices, including photoacoustic systems and phonon-communication networks. Here we introduce nanocrystal superlattices as a platform for phonon engineering. Using a combination of inelastic neutron scattering and modeling, we characterize superlattice-phonons in assemblies of colloidal nanocrystals and demonstrate that they can be systematically engineered by tailoring the constituent nanocrystals, their surfaces, and the topology of superlattice. This highlights that phonon engineering can be effectively carried out within nanocrystal-based devices to enhance functionality, and that solution processed nanocrystal assemblies hold promise not only as engineered electronic and optical materials, but also as functional metamaterials with phonon energy and length scales that are unreachable by traditional architectures.